Haensel



Jan. 31, 1956 v. HAENsEx. 2,733,193

SEPARATING AND CRACKING OF OIL FROM OIL-BEARING SANDS f'lege as Filed July 13, 1950 Fluid!! ed fafazyrf 36d Sayaf Occale United States Patent C) vSEPARATING AND CRACKING OIL FROM OIL-BEARING SANDS Application July 13, 195o, serial No. 173,498 i z Claims. (ci. 19e-s2) This invention relates to a continuous luidized method for carrying out simultaneously the separation and cracking of oil from oil-bearing sands, with the improved process being accomplished by contacting the oil-sands material with heated reactivated catalyst lparticles and recirculated heated oil-sand particles, which in turn are separated and returned in a controlled operation.

Various methods of handling tar or oil sands to recover the desired petroleum products have been utilized, as for example, hot water processing has been employed to remove the bitumen which has been adsorbed to the sand particles, and the bitumen is subsequently processed to obtain desired hydrocarbon fractions. Tar and oil sands have also been processed in the fluidized type of operation, with hot gaseous streamsA being introduced into a distilling and fluidizing zone to effect the vaporization of the hydrocarbon products. However, the use ofv high temperature flue gases for the distillation of the hydrocarbon from the oil sands is in general unsatisfactory in necessitating subsequent removal of large amounts of combustion gases from the vaporous products. The use of steam likewise necessitates the ultimate separation of hydrocarbon products from large quantities of4 water.

It isl the principal object of the present invention to etect simultaneously the separation of hydrocarbon materials from the oil sands and the catalytic cracking of the resulting hydrocarbon'vaporous materials within one contacting zone, so that a relatively large portion ofI the oil may be converted to more desirable low boiling products.

' It is also an object of the presentlinvention to provide means for effecting the continuousv distillation and cracking in one zone, and simultaneously a reactivation of catalyst particles in a regenerationzone together with the burning of residual carbon'aceous matter from sand particles, so that both catalyst andsand may be returned in a heated state to the conversion zone.

' Itis a still further object of the inventionto utilize advantageously uidized contacting within i separation and cracking zone, and liuidzation within a reactivation and burning'zone, to in turn effect an elutriation and classification between catalyst and inert sand particles, whereby catalyst and sand may be returned in selected quantities to the conversion zone.

Briefly, the present approved methodfor effecting the sparationand catalytic cracking of oil, from oil con taining sands, comprises,` introducing the 'oil sands in particulated forni to `a distillation and cracking zone together with a heated stream of particles consisting primarily of subdivided catalytic material, electing a fluidized contacting between the oil sands and the heated catalyst-containing particle stream within this cracking zone, discharging resulting hydrocarbon vapors from the upper portion of the distillation and cracking zone and withdrawing contacting solid material from the lowenend thereof; 4passing the withdrawnand contacted particles, withl a coke-"deposition thereon, to a burning andrclassif-l cation zone, introducing an oxygen-containing -stre'am 2 i into the latter zone and effecting therein a burningl of at least a major portion of the carbonaceous depositlfrom both the catalyst and sand particlesv while fluidizing and' passing said yoxygen-containing stream through lthe pai'' ticles in a lmanner effecting a classification thereof into an upperfluidized bed of primarily catalyst particlesand' a lower iluidized bed of primarily sand particles, removing resulting combustion Agases from the upper portion of the burning and classification zone while discharging a continuous stream yof santiparticlesV into the lower portion of the zone, and continuously withdrawing hot catalyst particles from the upper iluidized bed in the burning and classification zone' and returning them to the distillation and cracking zone, together with fresh oil sand particles as heretofore set forth. `j

By etiectingV the simultaneous processing steps within both the crackingrzone and the burning and classification zone, a relatively compact unit is providedV and a minimum of transfer lines is necessitated to carry out`the` continuous iiuidized operation. In other words, 'only two major contacting zones are utilized, with the separation and cracking of oil vapors being effected in a single confined conversion zone, and reactivation and heating together with the elutriation and classificationof particles being effected within a single confined regenerating and classification zone. The latter zone being operated to effect substantially distinct iiuidized beds of catalyst and sand particles and equipped with separate draw oli means, so that selected quantities of catalyst or sand may be discharged or withdrawn from the chamber` and selec-` tively returned to the conversion zone. v

Preferably, a catalyst having a density and vparticle size substantially different from that of the sand particles in the oil and tar sands is uitilized, such that the classification of particles within the reactivation and separating zone effects the maintenance of two` distinct layers of beds within the lower portion of that zone.v The'cra'cking catalyst mayy of course be any of the well known types of catalystl such as silica-alumina, silica-magnesia, silica-zirconia, or a natural catalystv such as Superliltrol, with the catalyst'particles' being maintained in alinely divded state' so'that theyreadily fluidize and maintain a light 'fluidizable' characteristic; The reactivation and classification zone has sufcie'nt air or oxygen-containing gaseous stream charged thereto 'so that luidization of all of the particles may `be maintained withinl `the lower *portion of the chamber and effect 'the desired elutriation and classification so `that the aforementioned distinct beds of particles are maintained. The reactivation zonel is also equipped .with two draw-off points, so that al sand-rich material may be withdrawn lfrom the lower end of` thel chamber wh'ile a catalyst-rich,y or sand-lean mixture, may be withdrawn from the upper portion or upp'er layerof the liuidized beds within the regenerator. Thusg' the major portion of the sand-rich layer may be withdrawn and discarded from theV operation while a subsequently rel activated catalyst stream may be continuously withdrawn' from the upper layer and returned tothe separation and cracking zone. A portion 'of the sp'entfsand-stream may of course be recycled to the separating 'and conversion zone togetherwith the catalyststream. The' quantities of recycled sand and' catalyst being governed by the heat requirements within the processing zone.

Inasmuch as some catalyst is of course lost with the sand-rich stream, which is discarded from the lower portion of the reactivation and classification zone, a small quality of fresh catalyst may be continuously added to the conversion unit to maintain a suitable catalyst to sand ratio for any desired separat-ion -and`cracking` reaction within the conversion zone. However,'thee1u'triation .and classcation'efected within'the regeneration zoneis preferably carried out in a manner' torholdthefcatalystlos's to a minimum, so that the necessary catalyst addition to the u'nit does not exceed (l5 lb`. per barrel of `o`il btiiid from the oil sand in the continuous operation.

The particle uidization and contacting within the separation and cracking z'one maybe eiected byany suit bleinertgaseu's .mediurm however, preferably the oil sand and catalyst particles `introduced into the separation and cracking zone are iluidized and maintained ina hinderedisettling bed type of contacting by a vaporous stream which comprises one .or more of the petroleum fractions obtainedfom the recovery of vapors and fractions disclirged-ffrom the upper portion of the cracking zone. The hydrocarbon vaporous stream, or recycle stream,pro vides auidizing stream which effects the desired coritac'tng between the catalyst sand particles and oil sand prtieles without necessitating an involved means of separation and recovery of hydrocarbons, as would steam or other inert gaseous mediums if used. l 4 Reference to the accompanying drawing and the following descriptions thereof will serve to more clearly illustrate the improved continuous kseparation and cracking process, as well as point out still further advantages in its operation.

Referring now to the drawing, there is indicated a distillation and cracking chamber 1, which in this instance is `illustrated as being supported at an elevated position above a lower regenerating and classifying chamber 2, so that the latter chamber may serve to support the upper and thus provide a more compact unit. Heated subdivided particles of catalystand spent sand are carried ina lluidized stream upward through riser line 3 to the lower portion of the cracking chamber 1. Crushed particles of oil sands arepassed from `a hopper 4 by way ofline 5 and control valve 6 to the riserline 3 so that the oil or tar-sand particles commingle with the hot catalyst and 4sand partiles to be subsequently. introduced into a iluidized bed of material maintained within the lower portion ofV the separation and cracking zone of chamber 1. The tluidized bed is indicated by the broken line 7.

A suitable uidizing stream, which may.be of an inert nature, or a hydrocarbon vapor stream, may be charged to the riser line 3. However, preferably a hydrocarbon vapor, such as a recycle fraction from the recovery end of the present cracking unit, is introduced at the lower end of the riser line 3 by way ofthe control valve ..8 so asto transport the heatedparticles of catalystand recycled sand material, together with the fresh oil sand ^particles into the cracking chamber 1, and also maintain the uidization-and intermixing of particles within the bed 7. A

distributing grid 9, in the lower-portion of chamberl, is

advantageous in `effecting a uniform distribution of the gas and particle stream into thelower portion of the chamber.

Contacting is effected Awithin the cracking chamber 1 in-amanner separating and distilling a major portion of the `hy'dx'ocarbonaceous material which adheres to the oil sand `in a .more or `less bituminous Istate. The heat for distillation and Aseparation of the bituminous material fromothe `oil sands is furnished -through the heat carried by both reciwrculated` catalyst and sand particles, as will be more -fully described hereinafter. The vaporized hydrocarbons are, however, contacted within the uidized lbed `7 by the catalyst material such that `a large portion ofthe `oil undergoes catalytic cracking, to provide lower Vboiling products of'a desirablenature. The resulting distillate and cracked vapors pass` from the upper end of the chamber 1 by way of a suitable mechanical or centrifugal separator, such as 10, with the substantially particle free vapors passing by way of line 11 and control valve 12 to suitable recovery and fractionating apparatus. The recovered solid `material is'r'etur'ned `:by wayof a suitable dipileglS-ioithe fluidized 7.

contacted particles, including boia fonia-orco .catalyst particles with La .carbonaceous deposit, Yand 4oil/sand, pav tieleswithiat least a majoripor'tion of the hydrocarbonavifzasnias ceous material removed by distillation, are continuously "withdrawn through a vsuitable withdrawal well 'as pro vided by a perforated baffle 14 and conduit 15. These particles in a preferred operation pass through a suitable stripping chamber 16, wherein steam or other inert gaseous material passes upwardly countercurrently to the particles and effects contacting and stripping of at least a large part of ilie absorbed hydrocarbon vapors which are adofbed or entrained with the descending particle stream. Stripping steam, or other material, may be introduced to,t hc lower end of the stripper-.16 by way of a suitable eofrdiiit 17 and control valve 18. The resulting strippedparticles of catalyst or sand are then passed by way of the standpipe 19 and control valve 20 into the lower portin of the regenerating and classifying chamber 2.

In accordance with the present invention, the regenerating and classifying chamber 2 will accommodate both catalyst and spent or relatively inert sand from the oil or tar-sands material, and burning is carried out within the` chamber by a suitable air or oxygen containing stream contacting the particles under fluidized conditions which effect simultaneously the oxidation and removal of carbon deposit and the elutriation or classification of material to effect a substantially satisfactory separation of catalyst from sand particles. The oxidizing and aerating Astream is introduced by way of line 2,1 and control valve 22, and a suitable distributing plate 23 in the lower portion of the chamber 2, whereby to effect fluidization of the particulated material passing by way of standpipe 19 into the lower portion of the chamber. As hereinbefore mentionecl, preferably a catalyst is used inthis combined operation which has substantially lower density and smaller particle size than the sand of the tar or oil sands, so that during the continuous fluidization of particles within the lower portion `of the chamber, a bed of the lighter catalyst particles is maintained as an upper layer or portioniwof the entire uidized bed,` the upper extremity being indicated by the broken line 24, while the upper extremity` of the fluidized bed vof sand particles is indicated bythe broken line 25. It should of course be understood that there -is no distinct line of demarcation between thetuidized sand and catalyst particles, Vbut that a gradiation occurs throughout tho emiro depth of the nuidized bod with primarily catalyst particles reaching the upper level of the bed and the lower portion of the bed comprisingprimarily sand.

The oxygen or air stream being introduced through line 21, may if desired be diluted with suitable inert gas, recycle flue gas, steam or the like, in `order to provide a sufficient quantity of tiuidizing gaseous mediumto effeet .the desired elutriation and` classification of particles within the dense phase bed of4 particles in the chamber 2. Preferably, the burning of the carbonaceous deposit on the catalyst particles and residual carbonaceous mat-' ter on thev sand vparticles effects the .desired heating'of particles which are to be recirculated through the cracking chamber 1 and provide the necessary heat therein for distillation of cracking. However, where it Amay be found economically desirable, additional heat may be introduced directly into the regenerating and classifying chamber 2 by way of aburner 26 receiving fuel and air through the lines 27 and 2'8'. Thus,.a close controlmy be maintained on chamber 2 to effect theheating of the particelsto any desired temperature, to in turnrnaintain a desired .heating and conversion balance throughout `thv: entire contacting unit.

The combustion on flue gases which result from thel reactivation and burning within chamber 2 are discharged by way of a suitable particle separator 29 and outlet line 30 with control valve 31. Recovered entrainedparticles arezreturned to the uidized bed 24 by wayof -a suit-able dipflegi-SZ. i

.'Itlis 1 .principal feature of .the .prsent L'rexottial and lclassifying operation to provide `'means for separately withdrawing `catalyst and sand -sti'earns from Athe lower portion of the contacting chamber.V A suitable particle draw off well is formed by a perforated baiile 33 at an intermediate level, so that a stream, primarily of catalyst particles may be withdrawn by way of conduit 34 and control valve 35, and introduced into the riser line 3. In addition, a withdrawal well is formed by a suitable perforated baffle 36 to provide means for Withdrawing a stream of primarily sand particles by way of conduit 37 and valve 38. A major portion of the sand-rich, or catalyst lean stream, passing by way of conduit 37 is discarded from the unit, however, in order to supply heat to the conversion chamber 1, at least a portion of the separated sand particles may be withdrawn by way of line 39 and valve 40 to subsequently become mixed with catalyst and oil-sand particles in the riser line 3.

By proper selection of catalyst particles with respect to size and density, it is possible to obtain a very good separation of catalyst and sand particles within the fluidized bed of the regenerating chamber, so that only a very small portion of catalyst is lost or discarded with the stream of primarily sand particles being discharged by way of conduit 37. However, in order to make up for the catalyst particles lost in this manner, as well as with the flue gas stream being discharged by way of separator 29 and line 30, provision is made by way of line 41 and control valve 42 for continuously introducing a small amount of catalyst into the contacting unit. Thus, a proper catalyst to oil, or to oil-sands, ratio may be maintained within the cracking chamber 1. As hereinbefore mentioned, the processing operation is preferably maintained to hold the catalyst loss to a miximum so that the catalyst addition is not too large and economically unsound, with fresh catalyst added to the unit being not more than about 0.5 of a pound per barrel of oil recovered from the oil-sands.

The apparatus arrangement which is shown in the present drawing is of course diagrammatic in that the present improved operation, with the simultaneous separation and cracking effected in the conversion chamber and the reactivation of catalyst effected in combination with the classifying operation, need not be carried out in this particular arrangement. For example, the position of one chamber over another is economically advantageous in permitting the gravity llow of particles from the upper zone to the lower zone and the elimination of fluidization or gas lifting to transfer particles to one of the two contacting zones. However, the regenerating and classifying chamber may if desired be positioned in the elevated position and the separation and cracking chamber maintained at a lower position, such that the reactivated and heated particles pass in a gravity flow to the conversion chamber, and conversely, the contacted catalyst and cilsand particles are carried upwardly by a liuidizing or gaslift stream, which in this instance would be the air or oxygen-containing stream.

Also, the present embodiment indicates the crushed oilsands particles passing from a hopper 4 into the riser line .3, but it is to be noted that the particles may pass vdirectly into the contacting and cracking chamber 1, and therein pass either concurrently or countercurrently to the fluidized bed of particles being composed of both catalyst and sand particles. Likewise, fresh catalyst may be added directly to the cracking chamber 1, rather than to the riser line 3 as indicated in the present drawing. Burners for additional heat, may of course be provided in connection with the cracking chamber 1, but in accordance with a preferred operation which utilizes two distinct and separate contact chambers, hot combustion gases are maintained only within the reactivation and classification chamber, so that all heat is carried to the cracking and conversion chamber by the particles and the liuidizng medium, with the latter being preferably a hydrocarbon vapor so as not to contaminate the resulting hydrocarbon vapors and bring about a subsequent separation problem in the fractionation and recovery section.

I claim as my invention:

l. A continuous method for simultaneously recovering and catalytically cracking hydrocarbons from subdivided particles of oil-sands, which comprises, introducing oilsand particles together with a rising stream of hydrocarbon vapors, obtained as hereinafter described, and heated particles of primarily a finely divided light catalyst into the lower portion of an elevated distilling and cracking zone, said catalyst particles being of lower density and smaller size than the sand of said oil-sand particles, passing the vaporous stream and subdivided particles upwardly through said zone and effecting a uidized contacting between said particles to distill hydrocarbonaceous vapors from said oil-sands and the cracking of said vapors within said zone, discharging resulting contacted hydrocarbon vapors from the upper portion of said cracking zone, withdrawing contacted solid particles comprising both catalyst and spent oil sand from said uidized bed of material maintained therein and passing it in a descending gravity ow through a stripping zone maintained at a lower elevation than said distilling and cracking zone, countercurrently contacting said particles within said stripping zone with a substantially inert heated stripping medium, subsequently passing the stripped catalyst and sand particles in a continuous gravity ow to an intermediate portion of a confined regenerating and classification zone, introducing a stream containing free oxygen to the lower portion of said regenerating and classification zone in a quantity and at a velocity sufiicient to maintain a uidization of said stripped particles within the lower portion of said regenerating and classification zone while simultaneously effecting both a burning of at least a major portion of the carbonaceous matter from both catalyst and oil-sand particles and an elutriation and classification between catalyst and sand particles, said light finely divided catalyst particles being maintained primarily in an upper bed above a uidized bed of heavier sand particles, discharging resulting combustion gases from the upper portion of said regenerating and classification zone, withdrawing a stream of primarily sand particles from the lower portion of the uidized bed of particles maintained within said regenerating zone, continuously withdrawing a heated stream of primarily catalyst particles from the upper portion of the fluidized bed of particles maintained in said regenerating and classication zone and commingling said stream with a hydrocarbon vapor stream comprising at least a portion of the cracked hydrocarbon vaporous stream discharged from the upper portion of the elevated distilling and cracking zone, subsequently commingling said hydrocarbon stream and regenerated catalyst particles with subdivided oil-sands and passing the mixture in a rising stream to the lower portion of said distilling and cracking zone as hereinbefore described.

2. The method of claim 1, further characterized, in that a portion of the withdrawn stream comprising primarily sand particles in the lower portion of said bed in said regenerating and classification zone is commingled with said catalyst and hydrocarbon vapor stream, whereby to supply additional heated particles to said distillation and cracking zone, and fresh linely divided catalyst particles are continuously added to said distilling and cracking zone to maintain a desired catalyst to oil-sand ratio therein at suitable cracking conditions.

References Cited in the le of this patent UNITED STATES PATENTS 2,355,016 Stein Aug. 1, 1944 2,423,674 Agren July 8, 1947 2,428,873 Gunness et al. Oct. 14, 1947 2,446,247 Scheineman Aug. 3, 1948 2,480,670 Peck Aug. 30, 1949 2,541,186 Anderson Feb. 13, 1951 2,561,396 Matheson July 24, 1951 2,573,906 Huff Nov. 6, 1951 2,627,499 Krebs Feb. 3, 1953 

1. A CONTINUOUS METHOD FOR SIMULTANEOUSLY RECOVERING AND CATALYTICALLY CRACKING HYDROCARBONS FROM SUBDIVIDED PARTICLES OF OIL-SANDS, WHICH COMPRISES, INTRODUCING OILSAND PARTICLES TOGETHER WITH A RISING STREAM OF HYDROCARBON VAPORS, OBTAINED AS HEREINAFTER DESCRIBED, AND HEATED PARTICLES OF PRIMARILY A FINELY DIVIDED LIGHT CATALYST INTO THE LOWER PORTION OF AN ELEVATED DISTILLING AND CRACKING ZONE, SAID CATALYST PARTICLES BEING OF LOWER DENSITY AND SMALLER SIZE THAT THE SAND OF THE SAID OIL-SAND PARTICLES PASSING THE VAPOROUS STREAM AND SUBDIVIDED PARTICLES UPWARDLY THROUGH SAID ZONE AND EFFECTING A FLUIDIZED CONTACTING BETWEEN SAID PARTICLES TO DISTILL HYDROCARBONACEOUS VAPORS FROM SAID OIL-SANDS AND THE CRACKING OF SAID VAPORS WITHIN SAID ZONE, DISCHARGING RESULTING CONTACTED HYDROCARBON VAPORS FROM THE UPPER PORTION OF SAID CRACKING ZONE, WITHDRAWING CONTACTED SOLIDS PARTICLES COMPRISING BOTH CATALYST AND SPENT OIL SAND FROM SAID FLUIDIZED BED OF MATERIAL MAINTAINED THEREIN AND PASSING IT IN A DESCENDING GRAVITY FLOW THROUGH A STRIPPING ZONE MAINTAINED AT A LOWER ELEVATION THAN DISTILLING AND CRACKING ZONE, COUNTERCURRENTLY CONTACTING SAID PARTICLES WITHIN SAID STRIPPING ZONE WITH A SUBSTANTIALLY INERT HEATED STRIPPING MEDIUM, SUBSEQUENTLY PASSING THE STRIPPED CATALYST AND SAND PARTICLES IN A CONTINUOUS GRAVITY FLOW TO AN INTERMEDIATE PORTION OF A CONFINED REGENERATING AND CLASSIFICATION ZONE, INTRODUCING A STREAM CONTAINING FREE OXYGEN TO THE LOWER PORTION OF SAID REGENERATING AND CLASSIFICATION ZONE IN A QUANTITY AND AT A VELOCITY SUFFICIENT TO MAINTAIN A FLUIDIZATION OF SAID STRIPPED PARTICLES WITHIN THE LOWER PORTION OF SAID REGENERATING AND CLASSIFICATION ZONE WHILE SIMULTANEOUSLY EFFECTING BOTH A BURNING OF AT LEAST A MAJOR PORTION OF CARBONACEOUS MATTER FROM BOTH CATALYST AND OIL-SAND PARTICLES AND A ELUTRIATION AND CLASSIFICATION BETWEEN CATALYST AND SAND PARTICLES, SAID LIGHT FINELY DIVIDED CATALYST PARTICLES BEING MAINTAINED PRIMARILY IN AN UPPER BED ABOVE A FLUIDIZED BED OF A HEAVIER SAND PARTICLES, DISCHARGING RESULTING COMBUSTION GASES FROM THE UPPER PORTION OF SAID REGENERATING AND CLASSIFICATION ZONE, WITHDRAWING A STREAM OF PRIMARILY SAND PARTICLES FROM THE LOWER PORTION OF THE FLUIDIZED BED OF PARTICLES MAINTAINED WITHIN SAID REGENERATING ZONE, CONTINUOUSLY WITHDRAWING A HEATED STREAM OF PRIMARILY CATALYST PARTICLES FROM THE UPPER PORTION OF THE FLUIDIZED BED OF PARTICLES MAINTAINED IN SAID REGENERATING AND CLASSIFICATION ZONE AND COMMINGLING SAID STREAM WITH A HYDROCARBON VAPOR STREAM COMPRISING AT LEAST A PORTION OF THE CRACKED HYDROCARBON VAPOROUS STREAM DISCHARGED FROM THE UPPER PORTION OF THE ELEVATED DISTILLING AND CRACKING ZONE, SUBSEQUENTLY COMMINGLING SAID HYDROCARBON STREAM AND REGENERATED CATALYST PARTICLES WITH SUBDIVIDED OIL-SANDS AND PASSING THE MIXTURE IN A RISING STREAM TO THE LOWER PORTION OF SAID DISTILLING AND CRACKING ZONE AS HEREINBEFORE DESCRIBED. 